Surface-active compounds



Patented Feb. 5, 1952 Ronald A. may. China Lake, CaliL, aasignor to TheProcter & Gamble Company, a corporation of Ohio No Drawing. ApplicationSeptember 8. 1949. Serial No. 114,680

10 Claims. 1 a

This invention relates to surface-active sulfonated compounds.

It is well known that surface-active properties, such as reduced surfacetension and high sudsing, washing and wetting power, are possessed byhigh molecular compounds which possess both hydrophilic and lipophilicgroups in proper balance, but some of these compounds are undesirablyexpensive while others, such as ordinary soap. are subject to thedisadvantages that they are destroyed by acid or are grained out bystrong salt solutions or are precipitated by alkaline earth or heavymetal salts such as are found in sea water and natural hard waters.

It is an object of this invention to provide new and inexpensivesurface-active agents. Another object is to provide washing, sudslng andwetting agents which are eiiective in soft, hard or salt water and donot form curd therein, and which can also be used in dilute acid oralkaline solution. Other objects will appear in the description whichfollows:

I have discovered a new class of surface-active detergents which aresubstantially unaffected by hard water or salt water and which can beused o radical derived from a saturated aliphatic hydrocarbon byremoving one hydrogen atom therefrom, and thus having the generalformula Canal and by an alkenyl radical I mean a univalent radicalderived in similar manner from an unsaturated aliphatic hydrocarbonhaving one double bond, the radical thus having the general formula Thefollowing specific examples illustrate compounds which ai'tersulfonation are included 25 within the scope of my invention.

even in dilute acids or alkalis. These surfaceactive agents are theproducts of sulfonating compounds of the general formula RCOXCnHmCOXYThe sulfonated compounds of my invention include both long chain fattyacid esters and amides, and may be further subdivided into diesters,diamldes, ester-amides and amide-esters.

; will be understood that when I speak of sulmated compounds" I use theterm broadly to lean the products obtained by treating these nsaturatedesters or amideswith strong suitoating agents such for example assulfuric acid, iming sulfuric acid, sulfur trioxide, chlorsulmic acid,and the like, and I do not attempt to efine the chemical structure ofthe resulting ilionated products because I am not in all cases ire oftheir structure. In some cases they apear to be true sulfcnates, i. e.having direct arbon-to-sulfur linkage, while in other cases ulfuricesters appear to be present, in which arbon is joined to sulfur throughan atom of xygen. The attack of the sulfonating agent is elieved to beat the olefinic bond in the alkenyl adical represented by Y in thegeneric formula. t may result in reactions such as these:

--CH===CH: CHzCHzOSOaH CHCH:

SOzH

-0 -CHOHCE:SO3H

' CHCH2OH OzH CHCH2SO:H

BOZH

It will be perceived that in the chemical foriulae proposed thehydrophilic portion is sit- .ated at the end of a long molecule, theother nd of which is lipophilic in nature, and this is elieved to be therequirement for pronounced urface activity. However, the utility ofthese cmpounds is in their proven surface activity, nd is not inherentin any particular speculative hemical structure which may be proposed asthe esult of the sulfonation process.

The esters and amides of my invention can be repared in a plurality ofways, some of which ill be described. I can, for example, start with ,naliphatic monohydroxy monocarboxylic acid, uch for example as glycollicacid or a lactic acid r a hydroxy butyric acid, which can be esteriledin conventional manner with an olefinic nonohydric aliphatic alcohol ofthree or four arbon atoms, such for example as allyl, meth- .llyl orcrotyl alcohol, 3-buten-1-ol, 3-buten-2- 1 and the like. The resultinghydroxy ester is hen acylated in conventional manner, as for xample bytreatment with an acid chloride, to cm a diester. Such reactions may berepreented thus:

1) HOCH2COOH+HOCH2CH=CH2+ HOCH2COOCH2CH=CH2+H2O 2)RCOC1+HOCHaCOOCH2CH=CH2- RCOOCH2COOCH2CH=CH2+HC1 Similarly, the amide ofan aliphatic monohylroxy monocarboxylic acid, such as the acidsdecribed' in the preceding paragraph, can be 'ormed in conventionalmanner, as for example 137 reaction of the methyl ester of the acid withLn aliphatic primary or secondary amine, one of .he valence bonds of thenitrogen of which is :atisfied by an alkenyl group of 3 or 4 carbonitems such as those of the alcohols mentioned n the preceding paragraph.The resulting hylroxy amide is then acylated in conventional manner toform an ester-amide. Such reactions may be represented thus:

( 1) HOCH2COOCH:+H2NCH2CH=CH2 HOCHzCONHCHzCH=CH2 CHaOH (2)HOCHzCONHCHzCH=CHa+ RCOC1+ RCOOCHzCONHCH2CH=CH2 +HC1 Diamides can bemade by amidifying a low molecular ester 01' an amino acid by treatingit with a fatty acid chloride; the resulting amide ester is then heatedwith an unsaturated primary amine to form the desired unsaturateddiamide. Such reactions can be represented thus:

( 1) RCOCi-i-HzNCIhCOOCHa- RCONHCHzCOOCI-h +HC1 (2) RCONHCHrCOOCI-Ia+H2NCH2CH=CHz- RCONHCH2CONHCH2CH=CH2+ CI'IJOH In generally similarmanner, amide-esters can be made by treating an amino acid with a fattyacid chloride to amidity the amino acid, and then esteriifylng with anunsaturated alcohol. Thus:

( 1) RCOC1+H2NCH2COOH+ RCONHCI-IzCOOH +HC1 (2)RCONHCHzCOOH-i-HOCHzCI-I=CH2 RCONHCH2COOCHzCH=CHz +H2O The followingexamples, in which all parts are by weight, illustrate the invention,but it is to be understood that they are illustrative only and that theinvention is not limited thereby but only by the terms of the appendedclaims.

Example 1.Allyl glycollate was prepared by mixing 94.5 parts ofcrystallized glycollic acid, 360 parts of allyl alcohol and parts ofbenzene, adding 2 parts of p-toluene sulfonic acid as catalyst, andboiling under reflux condenser for 10 hours. The solution was thenadjusted (by means of caustic soda and acid additions) until justcolorless to phenolphthalein, and was distilled under 48-50 mm. ofmercury pressure.

Most of the product distilled between 100 and 104 C. and was collectedseparately, the yield of distillate being 72% of that calculated astheoretically possible.

Allyl lauroyl glycollate was prepared by adding 85.8 parts of lauroylchloride dissolved in 101 parts of diethyl ether to 50 parts of theabove allyl glycollate dissolved in 99 parts of ether and 101 parts ofpyridine. The addition was slow, 38 minutes being required, during whichtime the temperature was maintained at 5-10 C. by external cooling.Stirring was continued for 2 hours at below 10 C. and thereafter thetemperature was allowed to rise to room temperature and stirring wascontinued for another 2 hours. Pyridine was then removed by washingsuccessively with water and 5% hydrochloric acid. Washing was thencontinued with water, with 1% sodium carbonate solution, and finallywith water again until again neutral. The product was then dried overanhydrous sodium sulfate and fractionally distilled between and 164 C.at about 3 mm. pressure. The weight of distillate indicated a yield of77% of theoretical.

Ester value and iodine value were respectively,

367 and 85.7, as against theoretical values of 377 and 85.

Allyl lauroyl glycollate was next sulfonated by adding simultaneouslyand at approximately equivalent rates (a) 30 parts of oleum containing59% free sulfur trioxide and (b) a solution of 30 parts of the aboveallyl lauroyl glycollate in 10 parts of ethylene dichloride to (c) 16.4parts of ethylene dichloride, with stirring and with aoaeivor externalcooling to keep the temperature below roughly equivalent streams of (a)technical 65% 40 C. Theaddition required about 10 minutes. oleum-containing 60% free sulfur trioxide by Seventy-six parts of the viscousacid paste were weight,the total amount or oleum being 47.5 parts.poured into ice water and the mixture was neuand (b) a solution of 50parts of the above allyl tralized below 50 C. by adding 28% sodiumhyamide of lauroyl glycollic acid in 80 parts of droxide solutionthereto slowly, with stirring, so ethylene dichloride to (c) a vesselcontaining 25.7 that the pH of the solution never rose substanparts ofethylene dichloride. During the mixing, tially above that of the methylorange endpoint. which required about 15 minutes, agitation was Theneutralized mixture was then extracted good and external cooling wasemployed, but the with petroleum ether to remove both unsulfonatmmixture became very viscous and the temperature ed organic matter andethylene dichloride. To rose to 35-40" C. the sulfonated product thuspurified, parts The viscous acid paste was neutralized and exof sodiumsulfate and 1.5 parts of disodium hytracted with petroleum ether as inExample 1. drogenv orthophosphate were added, and this The productpossessed marked wetting, sudsing mixture was adjusted to pH 7 and wasroll dried. and washing properties in medium hard and hard The driedproduct was surface-active and poswater, i. e. water of 7 and 21 grainsper gallon, sessed marked sudsing and washing power in forming no curdtherein at any concentration.

both medium and hard water, i. e. water of '7 Analysis of thealcohol-soluble portion of the grains per gallon and 21 grains pergallon, formproduct indicates that it was approximately one ing no curdtherein at any concentration. half monosulionate and one half asuliate-sul- Analysis of the alcohol-soluble portion of the fonate. asmay be seen from these figures:

Composition Per Cent Ester S0; 1 Per Cent Total 80;

CHHQSCOOCHIC ONHCHzCHOHCHaSOaNa 0 (Calc.) 19.2 (Calc.). C HuG 0 00310ONHCHzCH OSO;NaCH:SOaNa. l5. 4 Cale.) 30. 8 ECelGJ. Sulionation Productof Example 2 7. 5 ound) 24. 3 Found).

l This is the S03 determined by acid hydrolysis.

dried product indicated that it was approxi- Example 3.N-methallylhydroxy acetamide mately half monosulfonate and half a sulfatewasprepared by refluidng for 1 hour a mixture sulfonate, as may be seenfrom these figures: of 78 parts (110% of the theoretically requiredComposition Per Cent Ester SO; Per Cent Total SO:

cunncoocmcoocrncrioncmsome 0(Calc.) 19.1(Calc.;.

cunnooocmcoocmcnosomwmsmm..- 15.35(Calc.) 30.7(Calc..

Sulronation Product of Example 1' 7.1 (Found) 25. (Found).

1 This is the S 0; determined by acid hydrolysis.

Example 2.N-ally1 hydroxyacetamide was amount) of methallyl amine, 90.1parts of methyl prepared by dissolving 90.1 parts of methylhyhydroxyacetate and parts of methyl alcohol. droxyacetate in 50 partsof methyl alcohol, like- Sixty-two parts of this N-methallylhydroxyacetwise dissolving 60 parts of allylamine in 50 parts amide werethen dissolved in 70 parts of pyridine of methyl alcohol, and adding thelatter solution and 100 parts of benzene, the solution was cooled slowlyto the former while keeping the temperato 5 C., and 109 parts of lauroylchloride were ture below 40 C. The amount of amine was 50 added theretogradually in an hour's time, keep- 105% of the amount theoreticallyrequired to ing the temperature at 510 C. The mixture react with themethyl hydroxyacetate. The miX- was heated to 50-60 C. for 1 hour andwas washed ture was then boiled for 1 hour under reflux consuccessivelywith water, 5% hydrochloric acid,

' denser, and was evaporated to constant weight, water, and 1% sodiumcarbonate. It was then the yield being 114.4 parts, as against atheoretidried over Na2SO4 and the solvent was evaporated. cal yield of115.1 parts. The resulting viscous 50.5 parts of the above methallylamide of liquid contained 11.4% nitrogen and had an lauroyl glycollicacid dissolved in 158 parts of iodine value of 207.9, compared withtheoretical ethylene dichloride were sulfonated by adding 45 values of12.2 and 200 respectively. parts of technical oleum thereto while keep-The allyl amide of lauroyl glycollic acid was ing the temperaturebetween 35 and 45 C. Two prepared by adding 109 parts of lauroylchloride hundred forty-two parts of the viscous acid paste to a solutionof 55 parts of the above N-allyl were neutralized as in Example 1 andunsulfonhydroxyacetamide in 100 parts of benzene and ated organic matterwas removed by extraction 70 parts of pyridine. This addition requiredwith petroleum ether. 1% hours, during which time the mixture was To thethus-purified sulfonation product, 30 stirred and cooled to between 5and 10 C. The parts of sodium sulfate and 3 parts of disodium mixturewas gradually warmed, then heated at hydrogen orthophosphate were added,and this 50450 C. for 1 hour. After cooling it was washed mixture wasadjusted to pH 7 and was roll dried. successively with water, 5%hydrochloric acid and The resulting product possessed excellent wetting,1% sodium carbonate solution and was dried over sudsing and washingpower in both medium hard sodium sulfate. Volatile solvent was removedand hard water, i. e. water 01-! and of 21 grains by heating. The yieldwas of theoretical. per gallon, and formed no curd therein at any Theester value and the iodine value were redilution. The total SO: contentof the alcoholspectively 91% and 92% of theoretical. soluble portion ofthe product was 24.2%, which The above allyl amide of lauroyl glycollicacid 1 is good agreement with the corresponding values was sulionated byadding simultaneous and foundinExamples 1 ma.

1 'noolxounaoox'v I 1 bean those of from about 8 to. about .22 carbon,.toms.; Especially valuable products are obtained I vhenthe fatty acidsare chiefly lauric or myristic or the fatty acids from an oil of thecoconut oil I roup by which term I means to designate all 'egetable seedoils or fats at least '50per centby a, high de o completeness iofi i l ii Z i I 7 eight of the: combined fatty acids. of whichare auric and/ormyristic acids. These oils (many I samples of which are given in?HiIditcEsfThe j a I lh'emical Constitution of Natural. Fats". seconddltion :(1947), pages 198-205) arecommomydei .lved from seed of :membersof 1 the botanical I I amilies Laurace'ae (tangkallak. kernel oilioi'ex-i f f mple'); =Myristicaceae (ucuhuba nut .oil for i ex-;

.mple), Simaroubaceae (dika 1 Suit. oil for ex I a I mpiei jsalvadoraceaei :(Khakan: kernel oil so: i

" f xample) an'o moreiespecialiy; the Paimaefamilyg E 3 loconut oil istheoutstandinglexampleofanoil ierived'from'seed of. the Ealmiae family,butiother ion-limiting: examplgesof 'such'oils. areoils of j aurumurakernel, I tucuma kernel, cohune nut,

' Iuricoury nut, babassu kernelano'. palm kernel.

; mg acid; they make; the sulfonation; lessdrastic i i i vmre me man iamounts r unsaturated acids In'preparing the products hereincontemplated, I '-iavingtheformu1a"' iresent in the mixed; fatty acidsof oils of the 1 oconut oil group are not; seriously objectionable,

t is in general preierred that the fatty acids I p p i e derivedfromoils or fats iodinevalue 7 f j not substantially more than; 20. 1Substantial ab? ence of ethyleniic double bonds inthe' compoundsneansfewer side reactions during sulfonation. so f l 1 bat theproducts'obtained are asanue of better 1 olor and are better sudsing, washingand. wetting gents. I

While the acyls represented by RCO are comaonly those of fatty acidsderived from animal 1' vegetable oils, fats and waxes (all of which orconvenience I shall generically designate as fats") of low iodine valueor from those which lave been fully or partially hydrogenated,catlytically rearranged and/or grained or otherwise treated to reducetheir iodine value, synbetic fatty acids may also be used, suchfor-exmple as those obtained by oxidizing petroleum .ydrocarbons or byhydrogenating carbon monxide (the so-called Fischer-Tropsch process) rindirectly by oxidizing the saturated or unaturated hydrocarbons oroxygenated hydroarbons resulting from this process.

The value of n in the alkylene connecting link epresented by CnHZn inthe generic formula of my compounds, and the number of carbon atoms athe alkenyl radical represented by Y are varible small quantities,interrelated and dependent lso upon whether X and X are oxygen, NH rN(alkyl), and in the case of N(alkyl), upon he length of the alkylattached to the nitrogen. Vide choice is thus presented to one skilledin he art, and by combining these variables in suit- .ble manner,compounds varying in solubility, urface activity and usefulness may beobtained, epending upon the specific materials which are vailable andthe properties which are desired. :uch choice is however subject to thelimitation hat the products be water-soluble and that rhen dissolved inwater they possess surface-acivity. This criterion is easily applied byone killed in the art.

scribed can be accomplished with strong sulsuir'uric acid orsulfur'trioxide'. .Fuming sulfuric sulfonation. of the uiesters,diamides, esters amides or amide-esters which: have been de- 7 fona'tingagents such-for example as-98--'100/a acid isuchfor example asthatcontaining about j be :to 60%free'sulfur'trioxide by weight) is[especially suitable for the purpose since with 1 I, I it excessivesplitting of the fatty acid ester or g g :10

amide linkages does not occur nor are. there I excessive side reactions,the chief reaction being i i i at the double bond of the alkenyl grouprep're sented by Y. Inorder'toobtaingood color and I,

temperatures above 60C. should Dreferablybe order to. prevent localizedoverheating'at or near the point of contact of the sulfo'nating acidwith the: material to be .s uifonated, and aiso to i i i:prevent'locaiized excesses of the sulfonatlng acid. g T I Variousorganic solvents, 'diluents or; thinning; t i g 1 v agents may be; usedadvantageously during the i i i, i I 1 sulfonation, such for example asdioxane, .satu f i I r rated aliphatichydrocarbons,-chlorinated hydror gi y i i 1 carbons :and low molecular Eesters. Such 301-. 7 i i j i fvents, diluents or thinning agents are hfelpflul f f i I lreducingtheviscosityof the acid reaction mixg i g g i I i j i E'ture,thus making thorough: and; rapid ,mixing easier and preventing localexcesses of sulfonat;

andreduce side reactions, and they reducethe ,Y

tendency; or the sulfonating acid to splitfat ii 1 acidesterand amidelinkages. Specific examples i t 1 v i {of i such thinning agents are;hexane; heptane. i i I, i i i i ncarbon tetrachloride, andethylenedichloride; I 'Loweboiling saturated aliphatic esters-such .ioif.QI j example asmethyl and ethylacetates, are;espe-, i Q i I E ;ciallyeffective in dissolving both the materials to be sulfonated and thesulfonated products in order to give homogeneous solutions, in reducingviscosity, in rendering the reaction less drastic, in reducingundesirable side reactions, preventing splitting of ester-and amidelinkages, improving color, etc. Thus while at least 1.5 times as much,and preferably twice as much, ethylene dichloride as of material to besulfonated is required in order to give a mixture which is sufficientlythin to permit efiicient stirring, ethyl acetate is eifective when usedwith the material to be sulfonated in a weight ratio of only 1:1. Largeramounts of thinning agent are more effective but also more expensive.

For some purposes, the acid sulfonation mixture may be used withoutneutralization. More commonly, however, when the sulfonation reaction iscomplete the acid reaction mixture is neutralized, preferably at a lowtemperature not substantially above 50 C. When carboxylic ester groupsare present, splitting of such groups can be largely avoided byneutralizing to a final pH (at 25 C.) of about 5 to 8. Anyalkalinereacting compound may be used for this purpose provided its saltwith the sulfonic acid is water-soluble. Sodium hydroxide and itsalkaline salts, ammonium hydroxide, various amines, quaternary ammoniumbases, magnesium oxide or carbonate, etc. are illustrations of suchneutralizing agents. To avoid splitting fatty ester or amide linkages,adding the alkali slowly to the acid mixture is required, as well asefiicient mixing and cooling in order to insure against 10- calizedexcess of alkali or localized high temperature at any point in thereaction mixture.

The sulfonation products of the invention may be treated in conventionalmanner to remove unsulfonated organic matter, inorganic salts, etc., orthey may if desired be used without purifying. Conventional dryingmethods, such as drum drying, vacuum drum drying, spray drying and thelike may also be applied if desired. The physical character of theproduct, whether it be in bar, flake, granule, powder, paste, liquid orother form, is not a limitation upon the invention. Furthermore, theproduct may if desired be used in conjunction with soap or with otheranionic organic detergents (such for example as alkyl sulfates andsulfonates) or with non-ionic organic detergents (such for example asalkyl ethers of polyethyleneglycol or alkyl phenol ethers thereof orcorresponding thioethers) or with inorganic salts (such for example assodium sulfate, sodium chloride, sodium bicarbonate, mildly alkalinesodium silicate, sodium pyro-, tri-, tetraor metaphosphates and thelike) or with relatively unreactive organic compounds (such for exampleas fluorescin agents, carboxymethylcellulose, starch, urea, highmolecular aliphatic alcohols, fatty acid monoglycerides, fatty acidamides and the like). In general, however, combinations of water,'strongalkali and heating are to be avoided lest some splitting of the fattyester or amide linkage take place. It is especially advisable that whenthe sulfonated products are being heated during drying, the pH be near'7 and the heating be as brief and to as low a temperature as possible.

Having thus described my invention, what I claim and desire to secure byLetters Patent is:

1. The mixture of surface-active material which is the sulfonationproduct of a compound of the formula RCOXCnH2nCOX'Y where RCO representsacyl radicals of substantially saturated fatty acids of about 8 to 22carbon atoms, n is a small integer, X and X are selected from the groupconsisting of oxygen and N(Z), Z being a member of the group consistingof hydrogen and alkyl radicals of not more than 3 carbon atoms, and Y isa low molecular alkenyl radical, in which the carbon to carbon doublebond occurs at least one carbon atom beyond the carbon atom to which Xis attached.

2. A mixture of water-soluble surface-active salts of the sulfonationproducts of a compound of the formula RCON( Z) CnHimCOXY where RCOrepresents acyl radicals of substantially saturated fatty acids of about8 to 22 carbon atoms, n is an integer not less than 1 nor more than 3, Xis a member of the group consist-' where RCO represents acyl radicals offatty acids of about 8 to about 22 carbon atoms derived from fats havingan iodine value not substantially'more than 20, n is a small integer, Zand Z' are members of the group consisting of hydrogen and alkylradicals of not more than 3 carbon atoms. and Y is an alkenyl radical of3 to 4 cmbon atoms in which the carbon to carbon double bond occurs atleast one carbon atom beyond the carbon atom to which N(Z') group isattached.

4. A mixture of water-soluble surface-active salts of the sulfonationproducts of a compound of the formula RCOOCnHrnCOOY RCOOCnIIZnCON (Z) Ywhere RCO represents acyl radicals of fatty acids of about 8 to 22carbon atoms derived from fats having an iodine value not substantiallymore than 20, n is a small integer, Z is a member of the group consistinof hydrogen and alkyl radicals of not more than 3 carbon atoms, and Y isan alkenyl radical of 3 to 4 carbon atoms in which the carbon to carbondouble bond occurs at least one carbon atom beyond the carbon atom towhich the N(Z) group is attached.

6. A mixture of water-soluble surface-active salts of the sulfonationproducts of a compound of the formula RCOXCH2COX'CH2CH=CH:

where RCO represents acyl radicals of substantially saturated fattyacids of about 8 to 22 carbon atoms, and X and X are selected from thegroup consisting of oxygen and N (Z), Z. being a member of the groupconsisting of hydrogen and alkyl radicals of not more than 3 carbonatoms.

'7. A mixture of water-soluble surface-active salts of the sulfonationproducts of a compound of the formula where RCO represents acyl radicalsof fatty acids of about 8 to 22 carbon atoms derived from fats having aniodine value not substantially more than 20, X is a member of the groupconsisting of oxygen and N(Z'), and Z and Z are members of the groupconsisting of hydrogen and alkyl radicals of not more than 3 carbonatoms.

8. The mixture of sodium salts of the sulfonation products of a compoundof the formula RCON(Z) CHzCON( Z CHzCH=CHz RCOOCH2COOCH2CH=CH2 where RCOrepresents acyl radicals of fatty acids derived froman oil of thecoconut oil group, said salt being soluble in water and havingpronounced 3,5,701 11 12 ashing, sudsing and wetting power when inREFERENCES CITED ueous solution. V1118 10. The mixture of sodium saltsof the sulionai 5:: w m m of rd m the on pr of the UNITED STATES m'rmrrsncoocmcomz cn=cn=cm Number Name Date here RCO repmnts acyl radicals offat y acids ,173,1 9 ED513111 t, 31, 1939 arived from an oil of thecoconut oil group, and 3,184,770 Katzmm 26, 939 is a member or the groupconsisti ydr e 2, 36,541 Katzman Apr, 1, 1941 1d alkyl radicals of notmore than 3 carbon 10 ,359,4 Harris 0 1;, 21, 1941 ;oms, said salt beingsoluble in water and having 3,359,503 Baldwin o 1, 41 renoun ed washisudsing and wetting W 2,391,330 Jayne Dec. 25, 1945 hen in aqueousSolution.

RONALD A. HENRY.

1. THE MIXTURE OF SURFACE-ACTIVE MATERIAL WHICH IS THE SULFONATIONPRODUCT OF A COMPOUND OF THE FORMULA